Rubber Composition in Particular for the Manufacture of Tires

ABSTRACT

A rubber composition, in particular intended for the manufacture of tires, based on at least a predominant elastomer, chosen from the group consisting of butyl rubbers, essentially unsaturated diene elastomers, essentially saturated diene elastomers and the mixtures of these elastomers, and a reinforcing filler, characterized in that the composition also comprises at least one inert filler chosen from silicon-based lamellar mineral fillers and a nonfunctionalized polyisobutylene oil, having a molecular weight of between 200 g/mol and 40 000 g/mol, present in a proportion of between 2 and 50 phe.

The present invention relates to a rubber composition for themanufacture of tires and in particular for the manufacture of anair-impermeable internal layer, commonly known as “inner liner”, oftires.

This is because tubeless tires exhibit an internal surface of lowpermeability to air in order to prevent deflation of the tire and toprotect sensitive internal regions of the latter from admissions ofoxygen and water, such as plies comprising oxidation-sensitive metalcables, this protection making it possible to improve the endurance ofthe tire. Today, such protection of the internal surface of the tires isprovided by inner liners composed of elastomeric compositions based onbutyl rubber.

However, since savings in fuel and the need to protect the environmenthave become a priority, it is desirable to produce inner liners whichare impermeable to air and which exhibit a weight and a hysteresis whichare as low as possible, in order to obtain an improved rollingresistance of the tire. In point of fact, the performance in terms ofimpermeability to air of butyl rubbers is related to a not insignificantminimum thickness (of the order of a millimetre) and thus to a certainweight, which does not make it possible to efficiently respond to thesenew requirements.

Thus, it is necessary to add reinforcing fillers, such as carbon black,to the inner liner elastomeric composition in order to improve itsimpermeability. However, in a large amount, these reinforcing fillershave a detrimental effect on some properties of the composition, both inthe raw state: difficulty in working the raw composition, commonly knownas “processibility”, and in the cured state: deterioration in mechanicalproperties, in particular reduction in the flexural strength. Theintroduction of plasticizer of oil type makes it possible to overcomethese aspects of working and of mechanical properties but is very highlydisadvantageous to the impermeability.

Various solutions have been envisaged in order to overcome thesedisadvantages, in particular by resorting to other types of fillerswhich are additional to the reinforcing fillers, often known under thename of smectites and in particular of organophilic smectites. Theseorganophilic smectites improve the impermeability properties of thematerials if they are well dispersed in the material, that is to sayboth a homogeneous distribution of these fillers in the material andgood compatibility with the latter. This dispersion is often difficultto obtain due to the low thermodynamic compatibility existing betweenthe elastomers and such tillers.

The publication WO 20061047509 of the Applicant Company describes a tireinner liner composition, the composition of which, based on butyl rubberand comprising carbon black, comprises non-reinforcing fillers, whichare composed of organophilic smectites, which reduce the permeability ofthe gases, and which are dispersed in the elastomeric matrix, and aspecific plasticizer, which is composed of a terpene resin having inparticular a glass transition temperature Tg of greater than or equal to50° C. This composition indeed exhibits mechanical and impermeabilityproperties which render it acceptable for use as tire inner liner, byvirtue of the combined effect of these organophilic smectites and ofthis resin having a high Tg.

The Applicant Company has continued these research studies and hasdiscovered, surprisingly, that the combination, in a rubber compositionfor a tire inner liner, of a Is polyisobutylene elastomer of lowmolecular weight with organophilic smectites, in the presence of theelastomer conventionally used, such as butyl rubber, and of areinforcing filler, makes it possible not only to obtain properties ofprocessibility and of flexural strength which are as good as those ofthe compositions of the prior art but also to obtain improved propertiesof impermeability to gases and to significantly improve the propertiesof rolling resistance and of endurance without, of course, this being atthe expense of other properties.

As was mentioned above, oils are known for their property of improvingthe processibility but it is also known that they can be harmful to theleaktightness. It has been found here, surprisingly, on the one hand,that the combination of silicon-based lamellar mineral fillers and oflow weight polyisobutylene oil makes it possible to improve theleaktightness, including with respect to a conventional controlcomposition, and, on the other hand, that this composition also makes itpossible, at the same leaktightness with respect to the abovementionedorganophilic smectites/resin solution, to lower the hysteresis of themixture and thus to lower the rolling resistance of a tire having aninner liner made from this composition.

Thus, a subject-matter of the invention is a novel composition, inparticular for a tire inner liner, exhibiting properties ofimpermeability which are further improved with respect to theabovementioned solutions and an improved rolling resistance, without adeterioration in the mechanical properties of processibility and offlexural strength.

The invention relates to a rubber composition based on at least apredominant elastomer, chosen from the group consisting of butylrubbers, essentially unsaturated diene elastomers, essentially saturateddiene elastomers and the mixtures of these elastomers, and a reinforcingfiller, characterized in that the composition also comprises an inertfiller chosen from silicon-based lamellar mineral fillers and anonfunctionalized polyisobutylene oil, having a molecular weight ofbetween 200 g/mol and 40 000 g/mol, preferably between 500 g/mol and 35000 g/mol and more preferably still between 1000 g/mol and 30 000 g/mol,present in a proportion of between 2 and 50 phe.

According to an alternative embodiment of the invention, the predominantelastomer is composed of a butyl rubber and more particularly of acopolymer of isobutene and of isoprene or a brominated or chlorinatedpolyisobutylene.

According to another alternative embodiment of the invention, thepredominant elastomer is a diene elastomer and advantageously anessentially unsaturated or essentially saturated diene elastomer.

According to one embodiment of the invention, the predominant elastomerrepresents 100% of the elastomers of the composition.

According to another embodiment of the invention, the compositioncomprises one or more other elastomers chosen from the group consistingof butyl rubbers, essentially unsaturated diene elastomers, essentiallysaturated diene elastomers and the mixtures of these elastomers.

Advantageously, the silicon-based lamellar mineral fillers are chosenfrom phyllosilicates, these phyllosilicates preferably being chosen fromthe group consisting of smectites, kaolin, talc, mica and vermiculite.

The invention also relates to a tire article having a rubber compositionbased on at least a predominant elastomer, chosen from the groupconsisting of butyl rubbers, essentially unsaturated diene elastomers,essentially saturated diene elastomers and the mixtures of theseelastomers, and a reinforcing filler, characterized in that thecomposition also comprises at least one inert filler chosen fromsilicon-based lamellar mineral fillers and a nonfunctionalizedpolyisobutylene oil, having a molecular weight of between 200 g/mol and40 000 g/mol, preferably between 500 g/mol and 35 000 g/mol and morepreferably still between 1000 g/mol and 30 000 g/mol, present in aproportion of between 2 and 50 phe, and also relates to a tirecomprising such a rubber composition.

Finally, the invention relates to a process for preparing a compositionbased on at least a predominant elastomer, chosen from the groupconsisting of butyl rubbers, essentially unsaturated diene elastomers,essentially saturated diene elastomers and the mixtures of theseelastomers, and a reinforcing filler, characterized in that thecomposition also comprises at least one inert filler chosen fromsilicon-based lamellar mineral fillers and a nonfunctionalizedpolyisobutylene oil, the said process comprising the following stages:

-   -   incorporating in a diene elastomer, in a mixer:        -   a reinforcing filler,        -   an inert filler,        -   a polyisobutylene oil,    -   everything being kneaded thermomechanically, in one or more        goes, until a maximum temperature of between 110° C. and 190° C.        is reached;    -   subsequently incorporating:        -   a crosslinking system;    -   kneading everything up to a maximum temperature of less than        110° C.

I. MEASUREMENTS AND TESTS

The rubber compositions are characterized, before and after curing, asindicated below.

I-1. Mooney Plasticity

Use is made of an oscillating consistometer as described in FrenchStandard NF T 43-005 (1991). The Mooney plasticity measurement iscarried out according to the following principle: the composition in theraw state (i.e., before curing) is moulded in a cylindrical chamberheated to 100° C. After preheating for one minute, the rotor rotateswithin the test specimen at 2 revolutions/minute and the working torquefor maintaining this movement is measured after rotating for 4 minutes.The Mooney plasticity (ML 1+4) is expressed in “Mooney unit” (MU, with 1MU=0.83 newton.metre).

1-2. Tensile Tests

These tests make it possible to determine the elasticity stresses andthe properties at break. Unless otherwise indicated, they are carriedout in accordance with French Standard NF T 46-002 of September 1988.The “nominal” secant moduli (or apparent stresses, in MPa) are measuredin second elongation (i.e., after a cycle of accommodation) at 10%elongation (denoted “EM10”) and 100% elongation (“EM100”).

All these tensile measurements are carried out under the standardconditions of temperature (23±2° C.) and hygrometry (50±5% relativehumidity) according to French Standard NF T 40-101 (December 1979). Thebreaking stresses (in MPa) and the elongations at break (in %) are alsomeasured, at a temperature of 23° C.

I-3. Dynamic Properties

The dynamic properties ΔG* and tan(δ)max are measured on a viscosityanalyser (Metravib V Λ4000), according to Standard ASTM D 5992-96. Theresponse of a sample of vulcanized composition (cylindrical testspecimen with a thickness of 2 mm and with a cross section of 78.5 mm²),subjected to a simple alternating sinusoidal shear stress, at afrequency of 10 Hz, under the standard temperature conditions accordingto Standard ASTM D 1349-99, is recorded. A crest-to-crest strainamplitude sweep is carried out from 0.1% to 50% (outward cycle) and thenfrom 50% to 0.1% (return cycle). The results made use of are the complexdynamic shear modulus (G*) and the loss factor, tan(δ). The maximumvalue of tan(δ) observed (tan(δ)max) and the difference in complexmodulus (ΔG*) between the values at 0.15% and 50% strain (Payne effect)are shown for the return cycle.

I-4. Permeability

The permeability values are measured using a Mocon Oxtran 2/60permeability “tester” at 40° C. Cured samples in the form of discs witha predetermined thickness (approximately 0.8 to 1 mm) are fitted to thedevice and rendered leaktight with vacuum grease. One of the faces ofthe disc is kept under 10 psi of nitrogen while the other face is keptunder 10 psi of oxygen. The increase in the concentration of oxygen ismonitored using a “Coulox” oxygen detector on the face kept undernitrogen. The concentration of oxygen on the face kept under nitrogenwhich makes it possible to achieve a constant value, used to determinethe permeability to oxygen, is recorded.

An arbitrary value of 100 is given for the permeability to oxygen of thecontrol, a result of less than 100 indicating a reduction in thepermeability to oxygen and thus a better impermeability.

II. DETAILED DESCRIPTION OF THE INVENTION

The rubber composition according to the invention, based on at least apredominant elastomer (that is to say, for more than 50 phe), chosenfrom the group consisting of butyl rubbers, essentially unsaturateddiene elastomers, essentially saturated diene elastomers and themixtures of these elastomers, and a reinforcing filler, is characterizedin that it also comprises an inert filler chosen from silicon-basedlamellar mineral fillers and a nonfunctionalized polyisobutylene oil,having a molecular weight of between 200 g/mol and 40 000 g/mol, presentin a proportion of between 2 and 50 phe.

For the use thereof as inner liner of a tire, the composition comprises,as predominant elastomer, an elastomer chosen from the group consistingof butyl rubbers. However, the improved properties of leaktightness andof hysteresis of the compositions in accordance with the invention makeit possible to also recommend their use at other points in the tire(tread, sidewall, and the like) which predominantly use essentiallyunsaturated or saturated diene elastomers and/or mixtures of the latter.

Unless expressly indicated otherwise, the percentages shown in thepresent patent application are % by weight.

II-1. Elastomer or “Rubber”

Normally, the terms “elastomer” and “rubber”, which are interchangeable,are used without distinction in the text.

The composition in accordance with the invention intended for aleaktight inner liner of a tubeless tire comprises at least one butylrubber, used alone or as a mixture with one or more other butyl rubbersor diene elastomers.

The term “butyl rubber” is understood to mean a homopolymer ofpoly(isobutylene) or a copolymer of poly(isobutylene) with isoprene (inthis case, this butyl rubber is included among the diene elastomers) andthe halogenated derivatives, in particular generally the brominated orchlorinated derivatives, of these homopolymers of poly(isobutylene) andcopolymers of poly(isobutylene) and of isoprene.

Mention will be made, as examples of butyl rubber particularly suitablefor the implementation of the invention, of: copolymers of isobutyleneand of isoprene (IIR), bromobutyl rubbers, such as thebromoisobutylene/isoprene copolymer (BIIR), chlorobutyl rubbers, such asthe chloroisobutylene/isoprene copolymer (CIIR), and isobutylenerubbers.

By extension of the preceding definition, the name “butyl rubber” willalso include copolymers of isobutylene and of stirene derivatives, suchas copolymers of isobutylene and of brominated methylstirene (BIMS),among which is included in particular the elastomer called Exxpro soldby Exxon.

The term “diene” elastomer or rubber should be understood as meaning, ina known way, an (one or more are understood) elastomer resulting atleast in part (i.e., a homopolymer or a copolymer) from diene monomers(monomers carrying two carbon-carbon double bonds which may or may notbe conjugated).

These diene elastomers can be classified into two categories:“essentially unsaturated” or “essentially saturated”.

The term “essentially unsaturated” is understood to mean generally adiene elastomer resulting at least in part from conjugated dienemonomers having a level of units of diene origin (conjugated dienes)which is greater than 15% (mol %). In the category of “essentiallyunsaturated” diene elastomers, the term “highly unsaturated” dieneelastomer is understood to mean in particular a diene elastomer having alevel of units of diene origin (conjugated dienes) which is greater than50%.

Thus it is that diene elastomers, such as some butyl rubbers orcopolymers of dienes and of α-olefins of EPDM type, can be described as“essentially saturated” diene elastomers (low or very low level of unitsof diene origin, always less than 15%).

Given these definitions, the term diene elastomer, whatever the abovecategory, capable of being used in the compositions in accordance withthe invention is understood more particularly to mean:

-   (a)—any homopolymer obtained by polymerization of a conjugated diene    monomer having from 4 to 12 carbon atoms;-   (b)—any copolymer obtained by copolymerization of one or more    conjugated dienes with one another or with one or more vinylaromatic    compounds having from 8 to 20 carbon atoms;-   (c)—a ternary copolymer obtained by copolymerization of ethylene and    of an α-olefin having 3 to 6 carbon atoms with a non-conjugated    diene monomer having from 6 to 12 carbon atoms, such as, for    example, the elastomers obtained from ethylene and propylene with a    non-conjugated diene monomer of the abovementioned type, such as, in    particular, 1,4-hexadiene, ethylidenenorbornene or    dicyclopentadiene;-   (d)—a copolymer of isobutene and of isoprene (diene butyl rubber)    and also the halogenated versions, in particular chlorinated or    brominated versions, of this type of copolymer.

Although it applies to any type of diene elastomer, a person skilled inthe art of tires will understand that, for use as tire inner liner, thepresent invention is preferably employed with essentially saturatedelastomers, in particular of the type (d) above.

The following are suitable in particular as conjugated dienes:1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di(C₁-C₅alkyl)-1,3-butadienes, such as, for example, 2,3-dimethyl-1,3-butadiene,2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene or2-methyl-3-isopropyl-1,3-butadiene, an aryl-1,3-butadiene,1,3-pentadiene or 2,4-hexadiene. The following, for example, aresuitable as vinylaromatic compounds: stirene, ortho-, meta- orpara-methylstirene, the “vinyltoluene” commercial mixture,para-(tert-butyl)stirene, methoxystirenes, chlorostirenes,vinylmesitylene, divinylbenzene or vinylnaphthalene.

The copolymers can comprise between 99% and 20% by weight of diene unitsand between 1% and 80% by weight of vinylaromatic units. The elastomerscan have any microstructure which depends on the polymerizationconditions used, in particular on the presence or absence of a modifyingand/or randomizing agent and on the amounts of modifying and/orrandomizing agent employed. The elastomers can, for example, be block,random, sequential or microsequential elastomers and can be prepared indispersion or in solution; they can be coupled and/or star-branched oralso functionalized with a coupling and/or star-branching orfunctionalization agent. Mention may be made, for coupling to carbonblack, for example, of functional groups comprising a C—Sn bond oraminated functional groups, such as benzophenone, for example; mentionmay be made, for coupling to a reinforcing inorganic filler, such assilica, of, for example, silanol or polysiloxane functional groupshaving a silanol end (such as described, for example, in FR 2 740 778 orU.S. Pat. No. 6,013,718), alkoxysilane groups (such as described, forexample, in FR 2 765 882 or U.S. Pat. No. 5,977,238), carboxyl groups(such as described, for example, in WO 01/92402 or U.S. Pat. No.6,815,473, WO 2004/096865 or US 2006/0089445) or polyether groups (suchas described, for example, in EP 1 127 909 or U.S. Pat. No. 6,503,973).Mention may also be made, as other examples of functionalizedelastomers, of elastomers (such as SBR, BR, NR or IR) of the epoxidizedtype.

The following are suitable: polybutadienes, in particular those having acontent (molar %) of 1,2-units of between 4% and 80% or those having acontent (molar %) of cis-1,4-units of greater than 80%, polyisoprenes,butadiene/stirene copolymers and in particular those having a glasstransition temperature Tg (measured according to ASTM D3418) of between0° C. and −70° C. and more particularly between −10° C. and −60° C., astirene content of between 5% and 60% by weight and more particularlybetween 20% and 50%, a content (molar %) of 1,2-bonds of the butadienepart of between 4% and 75% and a content (molar %) of trans-1,4-bonds ofbetween 10% and 80%, butadiene/isoprene copolymers, in particular thosehaving an isoprene content of between 5% and 90% by weight and a Tg of−40° C. to −80° C., or isoprene/stirene copolymers, in particular thosehaving a stirene content of between 5% and 50% by weight and a Tg ofbetween −25° C. and −50° C. In the case of butadiene/stirene/isoprenecopolymers, those having a stirene content of between 5% and 50% byweight and more particularly of between 10% and 40%, an isoprene contentof between 15% and 60% by weight and more particularly between 20% and50%, a butadiene content of between 5% and 50% by weight and moreparticularly of between 20% and 40%, a content (molar %) of 1,2-units ofthe butadiene part of between 4% and 85%, a content (molar %) oftrans-1,4-units of the butadiene part of between 6% and 80%, a content(molar %) of 1,2- plus 3,4-units of the isoprene part of between 5% and70% and a content (molar %) of trans-1,4-units of the isoprene part ofbetween 10% and 50%, and more generally any butadiene/stirene/isoprenecopolymer having a Tg of between −20° C. and −70° C., are suitable inparticular.

Finally, the term “isoprene elastomer” is understood to mean, in a knownway, an isoprene homopolymer or copolymer, in other words a dieneelastomer chosen from the group consisting of natural rubber (NR),synthetic polyisoprenes (IR), the various copolymers of isoprene and themixtures of these elastomers. Mention will in particular be made, amongisoprene copolymers, of isobutene/isoprene copolymers (IIR),isoprene/stirene copolymers (SIR), isoprene/butadiene copolymers (BIR)or isoprene/butadiene/stirene copolymers (SBIR). This isoprene elastomeris preferably natural rubber or a synthetic cis-1,4-polyisoprene; use ispreferably made, among these synthetic polyisoprenes, of polyisopreneshaving a level (molar %) of cis-1,4-bonds of greater than 90%, morepreferably still of greater than 98%.

To Sum Up:

According to one embodiment of the invention: the predominant elastomerof the composition in accordance with the invention is a butyl rubber(in particular for applications as tire inner liners); the latter ispreferably chosen from the group of the essentially saturated dieneelastomers consisting of copolymers of isobutene and of isoprene andtheir halogenated derivatives, it being possible for this essentiallysaturated elastomer to be used as a mixture with an elastomer chosenfrom the group of the highly unsaturated diene elastomers consisting ofpolybutadienes (abbreviated to “BR”), synthetic polyisoprenes (IR),natural rubber (NR), butadiene copolymers, isoprene copolymers,butadiene/stirene copolymers (SBR), isoprene/butadiene copolymers (BIR),isoprene/stirene copolymers (SIR) and isoprene/butadiene/stirenecopolymers (SBIR) and the mixtures of these elastomers.

According to another embodiment of the invention, the predominantelastomer is an essentially unsaturated diene elastomer of thecomposition in accordance with the invention; the latter is preferablychosen from the group of the highly unsaturated diene elastomersconsisting of polybutadienes (abbreviated to “BR”), syntheticpolyisoprenes (IR), natural rubber (NR), butadiene copolymers, isoprenecopolymers and the mixtures of these elastomers. Such copolymers aremore preferably chosen from the group consisting of butadiene/stirenecopolymers (SBR), isoprene/butadiene copolymers (BIR), isoprene/stirenecopolymers (SIR) and isoprene/butadiene/stirene copolymers (SBIR).

In this embodiment, the diene elastomer is predominantly (i.e., for morethan 50 phe) an isoprene elastomer or an SBR, whether an SBR prepared inemulsion (“ESBR”) or an SBR prepared in solution (“SSBR”), or an SBR/BR,SBR/NR (or SBR/IR), BR/NR (or BR/IR) or also SBR/BR/NR (or SBR/BR/IR)mixture (mixture). In the case of an SBR (ESBR or SSBR) elastomer, useis made in particular of an SBR having a moderate stirene content, forexample of between 20% and 35% by weight, or a high stirene content, forexample from 35 to 45%, a content of vinyl bonds of the butadiene partof between 15% and 70%, a content (molar %) of trans-1,4-bonds ofbetween 15% and 75% and a Tg of between −10° C. and −55° C.; such an SBRcan advantageously be used as a mixture with a BR preferably having morethan 90% (molar %) of cis-1,4-bonds.

This embodiment corresponds in particular to compositions of theinvention intended to constitute, in the tires, rubber matrices ofcertain treads (for example for industrial vehicles), of crownreinforcing plies (for example of working plies, protection plies orhooping plies), of carcass reinforcing plies, of side walls, of beads,of protectors, of underlayers, of rubber blocks and other inner linersproviding the interface between the abovementioned regions of the tires.

II-2. Reinforcing Filler

Use may be made of any type of reinforcing filler known for itscapabilities of reinforcing a rubber composition which can be used forthe manufacture of tires, for example an organic filler, such as carbonblack, a reinforcing inorganic filler, such as silica, or a mixture ofthese two types of filler, in particular a mixture of carbon black andsilica.

All carbon blacks, in particular blacks of the HAF, ISAF or SAF type,conventionally used in tires (“tire-grade” blacks) are suitable ascarbon blacks. Mention will more particularly be made, among the latter,of the reinforcing carbon blacks of the 100, 200 or 300 series (ASTMgrades), such as, for example, the N115, N134, N234, N326, N330, N339,N347 or N375 blacks, or also, depending on the applications targeted,the blacks of higher series (for example, N660, N683 or N772), indeedeven N990.

In the case of use of carbon blacks with an isoprene elastomer, thecarbon blacks might, for example, be already incorporated in theisoprene elastomer in the form of a masterbatch (see, for example,Applications WO 97/36724 or WO 99/16600).

Mention may be made, as examples of organic fillers other than carbonblacks, of the functionalized polyvinylaromatic organic fillers asdescribed in Applications WO-A-2006/069792 and WO-A-2006/069793.

The term “reinforcing inorganic filler” should be understood, in thepresent patent application, by definition, as meaning any inorganic ormineral filler, whatever its colour and its origin (natural orsynthetic), also known as “white filler”, “clear filler” or even“non-black filler”, in contrast to carbon black, capable of reinforcingby itself alone, without means other than an intermediate couplingagent, a rubber composition intended for the manufacture of tires, inother words capable of replacing, in its reinforcing role, aconventional tire-grade carbon black; such a filler is generallycharacterized, in a known way, by the presence of hydroxyl (—OH) groupsat its surface.

The physical state under which the reinforcing inorganic filler isprovided is not important, whether it is in the form of a powder, ofmicrobeads, of granules, of beads or any other appropriate densifiedform. Of course, the term reinforcing inorganic filler is alsounderstood to mean mixtures of different reinforcing inorganic fillers,in particular of highly dispersible siliceous and/or aluminous fillersas described below.

Mineral fillers of the siliceous type, in particular silica (SiO₂), orof the aluminous type, in particular alumina (Al₂O₃), are suitable inparticular as reinforcing inorganic fillers. The silica used can be anyreinforcing silica known to a person skilled in the art, in particularany precipitated or pyrogenic silica exhibiting a BET surface and a CTABspecific surface both of less than 450 m²/g, preferably from 30 to 400m²/g. Mention will be made, as highly dispersible (“HD”) precipitatedsilicas, for example, of the Ultrasil 7000 and Ultrasil 7005 silicasfrom Degussa, the Zeosil 1165MP, 1135MP and 1115MP silicas from Rhodia,the Hi-Sil EZ150G silica from PPG, the Zeopol 8715, 8745 and 8755silicas from Huber or the silicas with a high specific surface asdescribed in Application WO 03/16837.

When the compositions of the invention are intended for tire treadshaving a low rolling resistance, the reinforcing inorganic filler used,in particular if it is silica, preferably has a BET surface of between45 and 400 m²/g, more preferably of between 60 and 300 m²/g.

In order to couple the reinforcing inorganic filler to the dieneelastomer, use is made, in a known way, of an at least bifunctionalcoupling agent (or bonding agent) intended to provide a satisfactoryconnection, of chemical and/or physical nature, between the inorganicfiller (surface of its particles) and the diene elastomer, in particularbifunctional organosilanes or polyorganosiloxanes.

Use is made in particular of silane polysulphides, referred to as“symmetrical” or “unsymmetrical” depending on their specific structure,as described, for example, in Applications WO 03/002648 (or US2005/016651) and WO 03/002649 (or US 2005/016650).

“Symmetrical” silane polysulphides corresponding to the followinggeneral formula (III):

Z-A-S_(x)-A-Z, in which:   (III)

-   -   x is an integer from 2 to 8 (preferably from 2 to 5);    -   A is a divalent hydrocarbon radical (preferably, C₁-C₁₈ alkylene        groups or C₆-C₁₂ arylene groups, more particularly C₁-C₁₀, in        particular C₁-C₄, alkylenes, especially propylene);    -   Z corresponds to one of the formulae below:

-   -   in which:    -   the R¹ radicals, which are unsubstituted or substituted and        identical to or different from one another, represent a C₁-C₁₈        alkyl, C₅-C₁₈ cycloalkyl or C₆-C₁₈ aryl group (preferably, C₁-C₆        alkyl, cyclohexyl or phenyl groups, in particular C₁-C₄ alkyl        groups, more particularly methyl and/or ethyl),    -   the R² radicals, which are unsubstituted or substituted and        identical to or different from one another, represent a C₁-C₁₈        alkoxyl or C₅-C₁₈ cycloalkoxyl group (preferably a group chosen        from C₁-C₈ alkoxyls and C₅-C₈ cycloalkoxyls, more preferably        still a group chosen from C₁-C₄ alkoxyls, in particular methoxyl        and ethoxyl),        are suitable in particular, without the above definition being        limiting.

In the case of a mixture of alkoxysilane polysulphides corresponding tothe above formula (III), in particular the usual mixtures availablecommercially, the mean value of the “x” index is a fractional numberpreferably of between 2 and 5, more preferably in the vicinity of 4.However, the invention can also advantageously be carried out, forexample, with alkoxysilane disulphides (x=2).

Mention will more particularly be made, as examples of silanepolysulphides, ofbis((C₁-C₄)alkoxyl(C₁-C₄)alkylsilyl(C₁-C₄)alkyl)polysulphides (inparticular disulphides, trisulphides or tetrasulphides), such as, forexample, bis(3-trimethoxysilylpropyl) orbis(3-triethoxysilylpropyl)polysulphides. Use is in particular made,among these compounds, of bis(3-triethoxysilylpropyl)tetrasulphide,abbreviated to TESPT, of formula [(C₂H₅O)₃Si(CH₂)₃S₂]₂, orbis(triethoxysilylpropyl)disulphide, abbreviated to TESPD, of formula[(C₂H₅O)₃Si(CH₂)₃S]₂. Mention will also be made, as preferred examples,of bis(mono(C₁-C₄)alkoxyldi(C₁-C₄)alkylsilylpropyl)polysulphides (inparticular disulphides, trisulphides or tetrasulphides), moreparticularly bis(monoethoxydimethylsilylpropyl)tetrasulphide, asdescribed in Patent Application WO 02/083782 (or US 2004/132880).

Mention will in particular be made, as coupling agent other thanalkoxysilane polysulphide, of bifunctional POSs (polyorganosiloxanes) orof hydroxysilane polysulphides (R²═OH in the above formula III), such asdescribed in Patent Applications WO 02/30939 (or U.S. Pat. No.6,774,255) and WO 02/31041 (or US 2004/051210), or of silanes or POSscarrying azodicarbonyl functional groups, such as described, forexample, in Patent Applications WO 2006/125532, WO 2006/125533 and WO2006/125534.

Finally, a person skilled in the art will understand that a reinforcingfiller of another nature, in particular organic nature, might be used asfiller equivalent to the reinforcing inorganic filler described in thepresent section, provided that this reinforcing filler is covered withan inorganic layer, such as silica, or else comprises, at its surface,functional sites, in particular hydroxyls, requiring the use of acoupling agent in order to form the connection between the filler andthe elastomer.

Preferably, the level of total reinforcing filler (carbon black and/orreinforcing inorganic filler, such as silica) is between 20 and 200 phe,more preferably between 30 and 150 phe, the optimum being in a known waydifferent depending on the specific applications targeted: the level ofreinforcement expected with regard to a bicycle tire, for example, is,of course, less than that required with regard to a tire capable ofrunning at high speed in a sustained manner, for example a motor cycletire, a tire for a passenger vehicle or a tire for a utility vehicle,such as a heavy duty vehicle.

For use of the composition as tire inner liner, use is preferably made,as reinforcing filler, of carbon black in a proportion of greater than30 phe. Preferably, the level of carbon black is between 30 and 120 phe;this is because, beyond this level, the disadvantages in terms ofstiffness of the composition are too great for application as tire innerliner. It is clear that carbon blacks of very high ASTM grade, such ascarbon black N990, are less reinforcing than carbon blacks of grade 700and a fortiori 600, and that it is necessary, for identicalreinforcement, to use higher levels of carbon black if carbon blacks ofgrade 900 are concerned than if blacks of grade 600 or 700 areconcerned.

More preferably, the proportion of carbon black is between 30 and 70phe; this is in particular the case when carbon blacks of ASTM grade 600or 700 are used and this proportion is more preferably still between 35and 60 phe.

The carbon black can advantageously constitute the sole reinforcingfiller or the predominant reinforcing filler. Of course, use may be madeof just one carbon black or of a mixture of several carbon blacks ofdifferent ASTM grades.

The carbon black can also be used as a mixture with other reinforcingfillers and in particular reinforcing inorganic fillers as describedabove, in particular silica.

II-3. Inert Filler

The term inert fillers is understood to mean non-reinforcing fillers,and silicon-based lamellar mineral fillers are more particularlysuitable here.

In particular, among silicon-based lamellar mineral fillers,phyllosilicates and particularly those included in the group consistingof smectites, kaolin, talc, mica and vermiculite are suitable.

Among the phyllosilicates, functionalized phyllosilicates and inparticular organomodified phyllosilicates are also suitable for theinvention. According to a specific embodiment, the organic structurewith which the inert filler is combined is a surfactant of formula:-M⁺R¹R²R³—,

-   -   where M represents a nitrogen, sulphur, phosphorus or pyridine        atom and where R¹, R² and R³ represent a hydrogen atom, an alkyl        group, an aryl group or an allyl group, R¹, R² and R³ being        identical or different.

In particular, organomodified montmorillonites are suitable for theinvention, thus montmorillonites modified with a surfactant, such as adihydrogenated dioctadecyldimethyl quaternary ammonium salt. Suchorganomodified montmorillonite is sold in particular by Southern ClayProducts under the trade names: Cloisite 6A and 20A.

Other surfactants based on quaternary ammonium salts can also be used tomodify phyllosilicates, such as described in Patent Application WO2006/047509.

This is because the abovementioned inert fillers are particularlyadvantageous as they make it possible to improve the impermeability ofthe compositions in which they are dispersed at a suitable level.

This inert filler is present in the composition in accordance with theinvention at levels ranging from 1 phe to 25 phe and preferably between3 and 15 phe.

II-4. Polyisobutylene Oil

The rubber compositions of the invention use an extending oil (orplasticizing oil), the usual role of which is to facilitate theprocessing, by a lowering of the Mooney plasticity, and to improve theendurance, by a reduction in the elongation moduli in the cured state.

At ambient temperature (23° C.), these oils, which are more or lessviscous, are liquids (that is to say, to recapitulate, substances havingthe ability in the long run to adopt the shape of their container), incontrast in particular to resins or rubbers, which are by nature solids.

Use is made, in accordance with the invention, of polyisobutylene oilswith a number-average molecular weight (Mn) of between 200 g/mol and 40000 g/mol. For excessively low Mn weights, there exists a risk ofmigration of the oil outside the composition, whereas excessively highweights can result in excessive stiffening of this composition. Theabovementioned polyisobutylene oils of low molecular weight havedemonstrated a much better compromise in properties in comparison withthe other oils tested, in particular with conventional oils of theparaffinic type.

Preferably, for the compositions in accordance with the invention, thepolyisobutylene oils have a molecular weight of between 500 g/mol and 35000 g/mol and more preferably still of between 1000 g/mol and 30 000g/mol.

By way of examples, polyisobutylene oils are sold in particular byUnivar under the “Dynapak Poly” name (e.g., “Dynapak Poly 190”), by BASFunder the “Glissopal” (e.g., “Glissopal 1000”) or “Oppanol” (e.g.,“Oppanol B12”) names, by Texas Petro Chemical under the “TPC” name (“TPC1350”) or by Innovene under the “Indopol” name.

The number-average molecular weight (Mn) of the polyisobutylene oil isdetermined by SEC, the sample being dissolved beforehand intetrahydrofuran at a concentration of approximately 1 g/l; the solutionis then filtered through a filter with a porosity of 0.45 μm beforeinjection. The device is the “Waters Alliance” chromatographic line. Theelution solvent is tetrahydrofuran, the flow rate is 1 ml/min, thetemperature of the system is 35° C. and the analysis time is 30 min. Useis made of a set of two “Waters” columns having the name “StyragelHT6E”. The volume of the solution of the polymer sample injected is 100μl. The detector is a “Waters 2410” differential refractometer and itsassociated software for making use of the chromatographic data is the“Waters Millenium” system. The average molar masses calculated arerelative to a calibration curve produced with polystirene standards.

The level of polyisobutylene oil is preferably between 2 and 50 phe.Below the minimum indicated, there is a risk of the elastomer layer orcomposition exhibiting a stiffness which is too high for someapplications, while, above the maximum recommended, a risk exists ofinsufficient cohesion of the composition and of loss of leaktightness,which may be harmful depending on the application under consideration.

The level of polyisobutylene oil is more preferably still between 5 and30 phe.

II-5. Various Additives

The rubber compositions in accordance with the invention can alsocomprise all or a portion of the usual additives generally used inelastomer compositions intended for the manufacture of tires orsemi-finished products for tires, such as, for example, otherplasticizing agents (other than the plasticizing system of theinvention), preferably non-aromatic or very slightly aromaticplasticizing agents, for example naphthenic or paraffinic oils, MES orTDAE oils, glycerol esters (in particular trioleates), especiallynatural esters, such as rapeseed or sunflower vegetable oils, pigments,protection agents, such as antiozonants, antioxidants or antifatigueagents, a crosslinking system based either on sulphur or on sulphurdonors and/or on peroxide and/or on bismaleimides, vulcanizationaccelerators, vulcanization activators or antireversion agents.

These compositions can also comprise, in addition to coupling agents,coupling activators, agents for covering the inorganic fillers or moregenerally processing aids capable, in a known way, by virtue of animprovement in the dispersion of the filler in the rubber matrix and ofa lowering in the viscosity of the compositions, of improving theirability to be processed in the raw state, these agents being, forexample, hydrolysable silanes, such as alkylalkoxysilanes, polyols,polyethers, primary, secondary or tertiary amines or hydroxylated orhydrolysable polyorganosiloxanes.

It is also possible to envisage the composition comprising other typesof filler, such as, for example, graphites.

II-6. Manufacture of the Rubber Compositions

The compositions are manufactured in appropriate mixers using twosuccessive preparation phases well known to a person skilled in the art:a first phase of thermomechanical working or kneading at hightemperature, up to a maximum temperature of between 110° C. and 190° C.,preferably between 130° C. and 180° C., followed by a second phase ofmechanical working up to a lower temperature, typically of less than110° C., for example between 40° C. and 100° C., finishing phase duringwhich the crosslinking system is incorporated.

The process in accordance with the invention for preparing a rubbercomposition for a tire inner liner comprises the following stages:

incorporating in an elastomer, during a first stage, at least areinforcing filler, an inert filler and a polyisobutylene oil,everything being kneaded thermomechanically, in one or more goes, untila maximum temperature of between 110° C. and 190° C. is reached;

subsequently incorporating, during a second stage, a crosslinkingsystem;

kneading everything up to a maximum temperature of less than 110° C.

These two stages can be carried out consecutively on the same mixer orcan be separated by a stage of cooling to a temperature of less than100° C., the last stage then being carried out on a second mixer.

By way of example, the first phase is carried out in a singlethermomechanical stage during which, in a first step, all the necessarybase constituents (elastomer, reinforcing filler and coupling agent, ifnecessary, inert filler and polyisobutylene oil) are introduced into anappropriate mixer, such as a normal internal mixer, followed, in asecond step, for example after kneading for one to two minutes, by theother additives, optional additional covering agents or processing aids,with the exception of the crosslinking system. After cooling the mixturethus obtained, the crosslinking system is then incorporated in anexternal mixer, such as an open mill, maintained at a low temperature(for example, between 40° C. and 100° C.). The combined mixture is thenmixed for a few minutes, for example between 2 and 15 min.

It should be noted that in particular when the predominant elastomer ischosen from butyl rubbers, the incorporation of the vulcanization systemtakes place on the same mixer as in the first phase of thermomechanicalworking.

The crosslinking system is preferably a vulcanization system based onsulphur and on an accelerator. Use may be made of any compound capableof acting as accelerator of the vulcanization of elastomers in thepresence of sulphur, in particular those chosen from the groupconsisting of 2-mercaptobenzothiazyl disulphide (abbreviated to “MBTS”),N-cyclohexyl-2-benzothiazolesulphenamide (abbreviated to “CBS”),N,N-dicyclohexyl-2-benzothiazolesulphenamide (abbreviated to “DCBS”),N-tert-butyl-2-benzothiazole-sulphenamide (abbreviated to “TBBS”),N-tert-butyl-2-benzothiazolesulphenimide (abbreviated to “TBSI”) and themixtures of these compounds. Preferably, a primary accelerator of thesulphenamide type is used.

Additional to this vulcanization system are various known secondaryaccelerators or vulcanization activators, such as zinc oxide, stearicacid, guanidine derivatives (in particular diphenylguanidine), and thelike, incorporated during the first phase and/or during the secondphase.

The final composition thus obtained is subsequently calendered, forexample in the form of a sheet or of a plaque, in particular forlaboratory characterization, or else is extruded in the form of a rubberprofiled element which can be used as tire inner liner.

The vulcanization (or curing) is carried out in a known way at atemperature generally of between 130° C. and 200° C. for a sufficienttime which can vary, for example, between 5 and 90 min depending inparticular on the curing temperature, the vulcanization system adoptedand the vulcanization kinetics of the composition under consideration.

The invention relates to the rubber compositions described above both inthe “raw” state (i.e., before curing) and in the “cured” or vulcanizedstate (i.e., after vulcanization).

III. EXAMPLES OF THE IMPLEMENTATION OF THE INVENTION

The examples which follow make it possible to illustrate the invention;however, the latter should not be limited to these examples alone.

Preparation of the Rubber Compositions

The tests are carried out in the following way: the reinforcing filler,the inert filler, the polyisobutylene oil, the butyl rubber and variousother optional ingredients, with the exception of the vulcanizationsystem, are successively introduced into an internal mixer, 75% filledand having an initial vessel temperature of approximately 60° C.Thermomechanical working is then carried out in one stage, which lastsin total approximately from 3 to 4 minutes, until a maximum “dropping”temperature of 140° C. is reached.

The mixture thus obtained is recovered and cooled and then sulphur andan accelerator of sulphenamide type are incorporated on an externalmixer (homofinisher) at 30° C., everything being mixed for anappropriate time (for example between 5 and 12 min).

The compositions thus obtained are subsequently extruded, either in theform of plaques (thickness of 2 to 3 mm) or of fine sheets of rubber,for the measurement of their physical or mechanical properties, orextruded in the form of tire inner liners.

Example

The object of this test is to show the improvement in performance of acomposition according to the invention in terms of rubber properties, incomparison with two control compositions of the prior art.

The three compositions A, B and C were prepared in accordance with theprocess described in detail in the preceding section and have the samefollowing base formulation 1, where the amounts are expressed in phe,parts by weight per hundred parts of elastomer:

Butyl elastomer (1) 100 Carbon black (N772) 50 Zinc oxide 1.5 Stearicacid 1.5 Accelerator (2) 1.2 Sulphur 1.5 (1) Brominated polyisobutyleneBromobutyl “3220”, sold by Exxon Chemical Co. (2) 2-Mercaptobenzothiazyldisulphide, MBTS.

The compositions A, B and C are defined as follows:

-   -   the control composition A is a “conventional” tire inner liner        composition not including inert filler,    -   the control composition B corresponds to the prior art of Patent        Application WO 2006/047509, which comprises organophilic        smectites and a plasticizing hydrocarbon resin with a Tg in        accordance with the characteristics of the said patent        application,    -   the composition C in accordance with the present invention        comprises an inert filler and a polyisobutylene oil of low        molecular weight at levels in accordance with the invention.

The formulation differences are presented in the following Table 1:

TABLE 1 Composition No. A B C Organophilic smectite (3) — 14.3 14.3Polyisobutylene oil (4) — — 10 Plasticizing resin (5) 10 (3)Functionalized montmorillonite “methyl tallow, bis (2-hydroxyethyl)quaternary ammonium”: “Cloisite 30B”, sold by Southern Clay (14.3 phe,corresponding to 10 phe of montmorillonite and 4.3 phe of surface-activeagents) (4) Polyisobutylene oil “Oppanol B12 SFN”, sold by BASF(molecular weight Mn = 25,000 g/mol) (5) Aliphatic resin (pure C5)“Hikorez A-1100” (Tg = 50° C., softening point 99° C.), sold by Kolon.

The rubber properties of these three compositions are measured beforecuring and after curing at 150° C. for 60 minutes. The results obtainedare given in Table 2.

TABLE 2 Composition No. A B C Properties before curing Mooney 68 53 52Properties after curing EM10 (MPa) 2.21 3.39 3.53 EM100 (MPa) 0.67 1.021.02 Breaking stress (MPa) 9.9 13.6 11.5 Elongation at break (%) 861 762669 Permeability to oxygen 100 65 61 Tan(δ)max-return cycle (60° C.-10Hz) 0.44 0.60 0.47

It is found that the composition C in accordance with the invention,comprising an inert filler and a nonfunctionalized polyisobutylene oilof low molecular weight, exhibits, in the raw state, a much betterprocessibility (lower Mooney) than the control composition A and onewhich is comparable with that of the composition B.

After curing, it is found that the composition C1 in accordance with theinvention exhibits a permeability which is markedly lower than that ofthe control composition A and also lower than that of the composition Bcomprising an organophilic smectite and a resin of high Tg, whichalready has a very good impermeability.

A slight increase with regards to the moduli obtained is observed forthe compositions B and C in comparison with the control A; however, thisincrease remains acceptable for the two compositions of the prior art Band in accordance with the invention C.

The properties of elongation at break and of breaking stress of thethree compositions A, B and C are comparable.

Finally, it is noted that the control composition A and the compositionin accordance with the invention C exhibit a similar value fortan(o)max, in contrast to the composition B, which has markedlydeteriorated in terms of hysteresis and thus, in the tire including aninner liner based on composition B, a poorer rolling resistance.

Thus, the composition C in accordance with the invention, including aninert filler and a polyisobutylene oil of low molecular weight, makespossible a strong improvement in the properties of leaktightness incomparison with a conventional control composition A and also incomparison with a control composition B already improved in terms ofleaktightness, without harmful deterioration in the other properties andwithout damaging the hysteresis, in contrast to the composition B.

1. A rubber composition based on at least a predominant elastomer,chosen from the group consisting of butyl rubbers, essentiallyunsaturated diene elastomers, essentially saturated diene elastomers andthe mixtures of these elastomers, and a reinforcing filler, wherein thecomposition also comprises at least one inert filler chosen fromsilicon-based lamellar mineral fillers and a nonfunctionalizedpolyisobutylene oil, having a molecular weight of between 200 g/mol and40 000 g/mol, present in a proportion of between 2 and 50 phe.
 2. Thecomposition according to claim 1, wherein the polyisobutylene oil has amolecular weight of between 500 g/mol and 35 000 g/mol.
 3. Thecomposition according to claim 1, wherein the polyisobutylene oil has amolecular weight of between 1000 g/mol and 30 000 g/mol.
 4. Thecomposition according to claim 1, wherein the predominant elastomer iscomposed of a butyl rubber.
 5. The composition according to claim 1,wherein the butyl rubber is a copolymer of isobutene and of isoprene. 6.The composition according to claim 1, wherein the butyl rubber is abrominated polyisobutylene.
 7. The composition according to claim 1,wherein the butyl rubber is a chlorinated polyisobutylene.
 8. Thecomposition according to claim 1, wherein the predominant elastomer is adiene elastomer.
 9. The composition according to claim 8, wherein thepredominant elastomer is an essentially unsaturated diene elastomer. 10.The composition according to claim 8, wherein the predominant elastomeris an essentially saturated diene elastomer.
 11. The compositionaccording to claim 1, wherein the predominant elastomer represents 100%of the elastomers of the composition.
 12. Composition according to claim1, which comprises one or more other elastomers chosen from the groupconsisting of butyl rubbers, essentially unsaturated diene elastomers,essentially saturated diene elastomers and the mixtures of theseelastomers.
 13. The composition according to claim 1, wherein thereinforcing filler comprises carbon black.
 14. The composition accordingto claim 13, wherein the level of carbon black is greater than 30 phe.15. The composition according to claim 13, wherein the level of carbonblack is between 30 and 120 phe.
 16. The composition according to claim13, wherein the level of carbon black is between 30 and 70 phe.
 17. Thecomposition according to claim 13, wherein the level of carbon black isbetween 35 and 60 phe.
 18. The composition according to claim 1, whereinthe reinforcing filler comprises a reinforcing inorganic filler.
 19. Thecomposition according to claim 18, wherein the reinforcing inorganicfiller is silica.
 20. The composition according to claim 1, wherein thelevel of polyisobutylene oil is between 5 and 30 phe.
 21. Thecomposition according to claim 1, wherein silicon-based lamellar mineralfillers are composed of phyllosilicates.
 22. The composition accordingto claim 21, wherein the phyllosilicates are chosen from the groupconsisting of smectites, kaolin, talc, mica and vermiculite.
 23. Thecomposition according to claim 21, wherein the inert filler is asmectite.
 24. The composition according to claim 23, wherein the inertfiller is a functionalized smectite.
 25. The composition according toclaim 21, wherein the inert filler is a kaolin.
 26. The compositionaccording to claim 21, wherein the inert filler is a talc.
 27. Thecomposition according to claim 21, wherein the inert filler is a mica.28. The composition according to claim 21, wherein the inert filler is avermiculite.
 29. The composition according to claim 1, which comprisesseveral inert fillers chosen from silicon-based lamellar mineralfillers, preferably from phyllosilicates.
 30. The composition accordingto claim 1, wherein the level of inert fillers is between 1 and 25 phe.31. The composition according to claim 1, wherein the level of inertfillers is between 3 and 15 phe.
 32. A tire article having a rubbercomposition according to claim
 1. 33. A tire inner liner having acomposition according to claim
 1. 34. A tire comprising a compositionaccording to claim
 1. 35. A process for preparing a rubber compositionbased on at least a predominant elastomer, chosen from the groupconsisting of butyl rubbers, essentially unsaturated diene elastomers,essentially saturated diene elastomers and the mixtures of theseelastomers, and a reinforcing filler, wherein the composition alsocomprises an inert filler chosen from silicon-based lamellar mineralfillers and a nonfunctionalized polyisobutylene oil, the said processcomprising the steps of: incorporating in a diene elastomer, in a mixer:a reinforcing filler, an inert filler, a polyisobutylene oil, everythingbeing kneaded thermomechanically, in one or more goes, until a maximumtemperature of between 110° C. and 190° C. is reached; subsequentlyincorporating: a crosslinking system; and kneading everything up to amaximum temperature of less than 110° C.
 36. The process according toclaim 35, wherein, between the thermomechanical kneading and theincorporation of the crosslinking system, the combined mixture is cooledto a temperature of less than 100° C.